Imidazole derivatives, useful especially as textile assistants and process of makingsame



5 NH-groupof an'imidazolewhichfon the one hand Patented June11,1935

nmnAzoLE DERIVATIVES,-USEFUL 'EsrE v CIALLY AS TEXTILE ASSISTANTS PROCESS; onMAKrNGse AND Charles Graenacher, Basel, and Franz Ackermann, Binningen, near Basel, Switzerland, as-

, signers to the firm Society of Chemicallndustry in Basle,Basel, Switzerland 7 No Drawing; Application May 25, 1934, Serial 1 No. 727,584.1111" Switzerland June 9,1933- 22 Claims. (01. 260-44) By the present invention new imidajzole derivativeswhich arevery yaluable as textileassistants are obtained bysubstituting by an alkyl o'raralkyl radical the {hydrogen atompf the is derived from a primary ortho-diamine and on the other hand is substituted at the ,u-carbon atom by an aliphatic or thydroaromatic radical containing at least 3 carbon atoms. The terms alkyl-* and 3 aralkyl-radica lsi as herein used are intended to include alkyland aralk'yl-radij cals substituted by hydroxyl, halogen, etc. Consequently the new products probably correspond to the generalformulav whereinX stands for an aromatic radical of the benzene or naphthalene series, wherein further the-two N-atoms are bound to two carbon atoms in ortho position, R1 represents an'aliphatic or hydroaromatic radical' containing at "least 3' carbon at0ms,-andR2 an alkyl or aralkyl radical,

' the terms alk'y andaralkyl radical as hereusedbeing intended to include substituted alkyl vor aralkyl radicals, as alreadymentioned above. Among these products those 3 are particularly valuablewherein the radical R1 means an aliphatic radicalconsisting of at least 8 carbon atoms, and R2 an aliphatic radical containing 2 .to'3' carbon atoms 'which-may be substituted by one or more hydroxyl groups. Also mixtures of such products among one another may have very particularly valuable efiects. T With strong acids, particularly 1 with hydrohalic acids, they form salts whose dilute-solutionsare .very capillary active. 'rFurther', they-possess also the property to combine with dyestuffs containing sulfogroups .to compounds which are generally" sparingly soluble. I w l r The substitution of the hydrogen atom of;the i'mino-group of an imidazole derivative of the kind above defined may be brought about by treating the parent imidine with an 'alkylating or aralkylating agent in. such amanner that merely the imidine hydrogen is replaced. This is best carried out by treating imidazole deriv- "atives of the'formula e are W e 1 wherein X and R1 have the meaning indicated above, with the alkylating agents which are quite generally capable of converting a secondary base, for instance dimethylamine, into a tertiary ammay be esters of alkyl or aralkyl alcohols, such as, for example, methyl iodide, methylbromide or methyl chloride, the corresponding ethyl, propyl, butyl, amyl and benzyl compounds and duce a1kyls containing 2 to 3f carbon atoms and,

' if necessary; one or more hydroxyl groups'i Such alkylating agents are ethyl chloride, ethylene chlorohydrine, ethylene bromohydrine, ac-glycerine chlorohydrine, epichlorohydrine and the like. The interaction takes place by heating the components in the presence or absence of a diluent.

ino compound. Such agents are well known and Or the alkyl-cr aralkyl radical canbe intro- 1 ducedbyi synthesizing the imidazole from apar ent' material which already contains thesubstituted nitrogen atom, For example, a secondary amine of the general formula aryl-NHR,

wherein-R. standspf'or alkyl or aralkyl and wherer in the aryl radical'contains an aminoor" riitr'ogroup in ortho-positio'n to the Nl-lR-group, "may be condensed with an aliphatic or 'hydroaromatic'carboxylic acid which contains at least nine carbon atoms, or with an ester of such'an acid, and then, if necessary after reduction of the intro-group, ring closure is brought about in known manner, for example, by heating, to form an imidazole derivative. Depending on the residuesuwithwhich they are substituted, the new -imidazole derivatives are colorless crystalline powders or semi-solid masses, whi ch in the form of their salts dissolve in'water to solutions which foam.. The new imidazoles find application in the tex- ,tile industry. and also in all other industries in which it is desired to cause or influence, preferably in an acid medium, alterations of colloidal or dissolved or undissolved phases. They are also valuable intermediate products for the manufacture of sulfonic acids and quaternary ammonium compounds according tothe process of "application Serial No. -66'l,133'."

The following examples illustrate the invention:--

Example 1 drobromide is thus obtained in-the-'form:of;a'

colorless crystalline powder which dissolves in acidified water to a clearesolutionzawhichzfoams strongly.

the corresponding ,u-heptadecyl-benzimi'dazoles monoalkylated at the nitrogen;atornnby-;using methyl chloride, ethyl chloride or .allyl bromide instead of ethyl bromide, whereby products having similar properties are obtained.

.l'7..8 .,parts .bf p-heptadecyl-benzimidazo1e are lheated-v with b, parts, of butyl chloride for-12 hours .-,at..1 60 J .inI-an autoclave. :The melt so obtained ,solidifies .,on-;coo1ingto a crystalline. mass Which v ,dissolv.es in :hot tacidi swhich. ,foams strongly.

Ea'ample 3 67.2. partsof @a ,mixture of ,u-pentadecyl-and t heptadecylsbenzimidazole,' obtainable by heat- .35 ,ingacommercialrstearic-racid -.--withortho phenyl- .Ienediamine, are :meltedand heated to 125 C. Then ..25,.2".;,parts- .ofadiinetlnzl "sulfate are :added fi radually-ito-the melt-zand the reaction mixture .is-iheated until. ,a-.test rsample dissolves in acidi- 140 :fied water to -a'- clear solution. zThereactionmass rittle product which canweasily .,.be,-p.owdere.d.

'7 \6.7.2 parts =ofthe-1hixture -of- -pentadecyl and -,u.heptadecyl-benzimidazolereferred to in Example-3 and 25.3-parts,of-,benzyl chloride are stirred -together .at I .-1 45.l50 0., whilst excluding air. -,inixt ure {is-kept latwthis temperature for 10 hours, whereby apale yellowish .oil is obtained whichsolidifies ,at rooz'n temperature-town ex- .tremely -tough resinous mass. By recrystalli- -.zation,-ofv.the mass from chlorobenzene, there is -..obtained a.mi xture of .the Nsbenzylated benzimid- --azolehydrochlorides .in the form or a color- ;less crystalline powder ,which is soluble to some .extentinv hot water-acidified with hydrochloric .acid. 7 i I Example-5 ..3,l0 par.ts of heptade cenyl-benzimidazole, ob- ..tained by heatingLortho-phenylene diamine to- .,gether .with olive oil, are stirred at 12Q-.125 C. with..96 partsaof ethylene chlorh-ydrine, prefer- ,abl;y-in,;an zatniospherefree of oxygen, until a test sample of the reaction mixture dissolves to a, clear solutiouin water acidified with .hydro- ..ch1oric .acid. reactionproduct, which conlsists ,chiefiyof the hydrochloride .of N-hydroxy- ;ethyle i-heptadecenyl-benzimidazole, is a viscous,

.brownish oil :at ordinary temperature.

as Parts of misiWa i-beea nid z esa k In an analogous manner there are obtained fied water to a solution 3 ated at the i-carbon atom by higher alkyl radicals, obtained by heating ortho-phenylenediamine with hydrogenated fish oil, are heated with parts of ethylene chlorhydrine at -130 C. :for 871101115, 'air being excluded.- pflhere is ob- :tained at brownish oil which solidifies on cooling to a soft mass which dissolves in acidified water [.itO a clear solution which foams strongly.

" L;;Ea:ample 7 10 "1'0 parts of t-heptadecyl-benzimidazole are heatedawithiz parts of ethylene oxide at 200 C. eforrla0-shoursiinian autoclave. There is obtained saintly brownish oil which solidifies at ordinary temperature to a solid, wax-like substance 1,anddissolvesto.axclear solution in water to which ehasbeenyadded,agsmall quantity of hydrochloric acid.

-17 8-parts of t-heptadecyl-benzimidazole are a ,heated to 1201125,;'C.=whereupon there are .-added v gradually; while stirring, 60 parts of za-glycerine- .7 chlorhydr-ine. Thereaction lmixtureis, then'heated gradually to C..-and;mai;ntained;at.-this:temperature until a test sample of the reaction mass 3 dissolves to a completelygclear solution in acidified water. The reaction-product, which is oily at a raised temperature solidifies at room temperature to a mass which resembles ointment and is soluble also in organic solvents, such as alcohol, glyc- 4 ,qerine and benZene.

I EwampZe/IJO 31;parts-of;a; benzinudazole; .obtainedbyheating 4&5 :orthmpheriylenediamine WithflllISBGd bill-are heat- ...ed .at -1-.6,0 Crier 8 hours with 9=6.;19arts =.of ngl-yoer-ine-chlorhydrine, aim-being excluded. "There is obtaineda product havingiproperties similar to .thoseof; the-reaction:mass describ ed-in:Example;8. .50

- z-Emmivie 11 510 partsrof/a-heptadecyl-kamino-benziniidazole ,(made by condensation ofqpa-raenitrophenylene- 9.5.5 diamine with :steariczacidand subsequent: rreducstion ;of.-.the condensation product) and. 5.0 :parts'of -zethyleneechlorh-ydrine are hea ted :to :boilingqina reflux apparatusuntila test sample.;of;the .-re- .action mass dissolyesvreadily -inwater to .a clear s60 ..solution. After the excess of 'ethylene-chlorhy- ..drine hasqbeen 1distilled',.:there.remains a :brownisli oily reaction product which forms-solutions which foam strongly. i l

Ezmmple 12 17:8 parts of -.Mheptadecylsbenzimidazole are theated ,with parts: oftmonochloracetic;acid.ethyl ester atul30-slt0'f-rCnwithrexclusioniofair, until a test sample of the. reactionrmass;:dissolves in acidified water to a clearsolution. After cooling, the mass solidifies toajcrystalline cake of i-heptadecyl-benzimidazole-Niaceticacid-ethyl ester hydrochloride. By treating the ester so obtained it? -witha wsaponifying agent, such as ani alcoholic caustic soda solutin,:there is obtained the-sodium salt of e-hepta'decyl-benzimidazole-N-aceticl acid in the form of a colorless crystalline ipowder which dissolves readily in'lwater to alsolution' eircellent whichfoams strongly. The product has levelling properties.

E wampl e parts of the product of the action eta-glycerine-chlorhydrine on heptadecyl-benzimidazole, the preparation of which isdescribed in Example 9,, and 10 parts of the pI'OdllCt'OfrthQfiCtiOH of ethylene chlorhydrine- .on the mixture of benaimidazoles from hardened fish-oil and orthophenylenediamine, the preparation of which is described in Example 6, are1melted-together;at 1&0? C. whilstexcluding air. On cooling the mixture there is obtained a viscous semi-solid mass whose aqueous solutions are more stable than the aqueous solutions of the individual components.

Example 14 There are mixed together 100 parts of a mixture of benzimidazoles substituted at the ,u-carbon atom by higher alkyl-groups, obtainable by heating together ortho-phenylene-diamine', and hy-s of ortho-phenylenediamine areheated together 1 p at 220-240 C. whilstexcludirigair, until a sample" ZS benzimida zole (preparedfrom ortho phenylenediamine and olive oil) and parts of a mixture oftbenzirnidazoles-consisting of the i-nonyl the a-undecvl, the ,u-tridecy lfl the p-pent adecyl and the -heptadecenyl-benzimidazoles prepared by heating ortho-phenylenediamine and coconut oil.

ture dissolves to a clearsolution in cold water. 'There is obtained a very "viscous brownishfloil which dissolves to "completely clear solutions in water andin alcohol; i It's aqueous solutionsare' stable; especially on-the addition of some acid or 0f??? alcohol l i I mammals;

restarts anydagetaad fish oil, 240 p artsof 3 olive oil, 239 parts of coccnut oil and363 parts of the reaction mass is found to be free from ortho-phenylenediamine; this-requires about 18 hours. The reaction :product'is now allowed to cool to C., whereupon there is allowed to run in gradually a; mixture of parts :of ethylene chlorhydrine-t-and 200, parts of a-glycerine- ,jcl1lorhydrine. '1'; l A

The reaction mixture is heated for some :time

with exclusion of air, after which the tempera- There is thus obtaineda tough brownish mass whose properties resembleithose of the product Q r J A -wh'ere inR1 represents'an aliphatic radical condescribed in Examplei'l l-n {The process is similar with other diamines possessing adjacent NHzgroups, such as, for example, toluylenediamine,

derivatives, consisting in heating; imidazole .de-

rivatives of the general formula i \C- R1 Q v v E A wherein ,Xstands. for an aromatic radical, of the benaene or naphthalene series, wherein further the two N-atoms are bound to two carbonatoms in ortho-ppsition, and R1 represents an aliphatic radical containing atleast 8, carbon atoms, with such 'alkylating agents which introduce ,alkyl radicals containing as substituents none but OH-groups.

2. A process for the manufacture of. imidazole derivatives, consisting in heating imidazole de rivatives of the general formula wherein R1 represents lan ali p ha tic radical containing at least 8 carbon atoms, with such alkylating agents which introducealkyl radicals containing as substituents none but OI-I-groups.

3. A process for the manufacture of imidazole derivatives, consisting in heating imidazole derivatives of the general formula wherein R1. represents" radical con- :tainingv at least 8 carbonatomswith such alkylating agents which introduce alkyl. radicals con-.

taining ias substituents none but oH-groups.

4AA process 'forthe manufacture of imidazole derivatives,consisting in heating imidazole derrivatives of thegeneral formula i wherein R1 representsfan aliphat1cradicall-containing at least 8 carbon atoms, with such alkylating agents-which introduce alkyl radicals containing as substituents none but OH-groups and themselves contain not more than 3 carbon atoms.

5. A process'for the manufacture of imidazole derivatives, consisting in; heating imidazole del g rivatives of the general formula at 120-125 C. with continuous,slowjstirring and 1 taining at least 8 carbon atoms, with suchalkylating agents which introduce "alkyl radicals containing as substituents none but 0H-groups and themselves contain not more than 3 carbon atoms and at least one hydroxyl-group.

6. A process for themanufacture of imidazole -derivatives,:iconsisting :in iheatingfiirnidazolerde rivatives of the general formula WhereinfBr represents an' aliphatic radical .containing at least 38 carbon atoms, with ethylene chlorohydrine.

"7. A. process "for the manufacture of-imidazole .deriva'tives, consisting in heating imidazole derivatives of the general formula wherein R1 represents an aliphatic radical coni taining at least 8 carbon atoms, with glycerine chlorohydrine.

8. A process for the manufacture of imidazole derivatives, consisting in heating imidazole derivatives-of the general formula I v r "and 'the -heptadecenyl-benzimidazoles, with glycerine chlorohydrine.

11. A process forsthe manufacture of imidazole derivatives, consisting in heating the imidazole derivative prepared by heating ortho-phenylenediamine with stearic acid, with methyl chloride. 12. The imidazole derivatives of the general wherein X stands Jforan aromatic radical of the benzene or naphthalene series, whereinfurther the two N-atoms are bound-to two carbon atoms in ortho-position, R1" represents an aliphatic radical containingatleast 3 carbon atoms, and R2 an aliphatic or araliphatic radical, which products form with hydrohalic acids salts whose dilute aqueous solutions are strongly capillary active.

13. Theimidazole derivativessof the general formula 1 wherein R1 represents an aliphatic iradical iconvitaining at ileast i8 :;ca'rbon atoms,-iand;Rz :anialiiphatic; orxaraliphaticxradical,iwhiohiproducts form :withzhydrohalici'acidszsalts'whose dilute aqueous :solutionseare stronglycapillary active.

;14.;The iimidazole derivatives 1 of rthe "general formula v I I V v 1 whereinRr'represents an aliphatic radical con 'tainingatleast8 carbon atoms, and R2 an*'a1i phatic radical, which products-form with hydrohalic acids salts whose dilute aqueous solutions rare strongly capillary active.

15. The imidazole derivatives of the general "formula 'wherein- R1 represents an "aliphatic radical containing at least 3 carbon-atoms-and R2 an' aliphaticradi'cal containing notmore than 3carbon atomsywhich" products form with hydrohalic acids salts -whose dilute aqueous solutions are strongly capillary active.

16. The imidazole derivatives of the general formula cwhereinrRl represents an aliphatic'radical'containing at .least.-'-8'carb'on atoms,-.and. R2 an aliphatio radical containing not more than :3 carbon atoms and at least 'one OI-I-group, which products form with hydrohalic acids salts whose dilute aqueous solutions are strongly capillary active.

, .17. The aimidazole derivatives of the general formula v wherein R1 represents an aliphatic radical con- -taining at least 8 carbon a'toms which products form with hydrohalic acids salts whose dilute aqueous'solutions are 'strongly capillary active.

-18.'The imidazole derivatives ofthe general I 'formula' Y ta t-L0H wherein. R1 represents an aliphatic rradical containing at least 8 carbon atoms, :which products form with hydrohalic acids salts whose'fdilute :aqueous': soiutionszaresstrongly:capillary ,active.

formula wherein Ry-represents an aliphatic radical containing at least 8 carbon atoms, which products form with hydrohalio acids salts whose dilute aqueous solutions arestrongly capillary active.

20. The imidazole derivative mixture of f the general formula l a HrGHnOH wherein represents the nonyl-, the'undecyl-,

I 5 21; The imida'zole derivative mixture of the general formula N/H H2 her- 5- --0H p p H wherein R1 represents the nonyl-, the undecyl-, the tridecyl-, the -pentadecyb, and the ,u-heptadecenyl-radica1,- which products form with hydrohalic acids salts whose dilute aqueous solutions are strongly capillary. active. 22. The'imidazole derivative of the formula which product forms with hydrohalic acids salts whose dilute aqueous solutions are strongly 

